Recyclable Oxofluorovanadate‐Catalyzed Formylation of Amines by Reductive Functionalization of CO 2 with Hydrosilanes

An efficient method has been developed for the reductive amination of CO 2 by using readily available and recyclable oxofluorovanadates as catalysts. Various amines are transformed into the desired N ‐formylated products in moderate to excellent yields at room temperature in the presence of phenylsilane. Mechanistic studies based on in situ infrared spectroscopy suggest a reaction pathway initiated through F−Si interactions. The activated phenylsilane allows for CO 2 insertion to produce phenylsilyl formate, which undergoes attack by the amine to generate the target product.